Preparation and reactivity of stannyl and germyl complexes of cobalt

Trichlorostannyl complex Co(SnCl 3)(CO) 2(PPh 3) 2 (1) was prepared by allowing the chloro compound CoCl(CO) 2(PPh 3) 2 to react with SnCl 2·2H 2O. Instead, treatment of the iodo complex CoI(CO) 2[PPh(OEt) 2] 2 with SnCl 2·2H 2O afforded a mixture of Co(SnCl 2I)(CO) 2[PPh(OEt) 2] 2 (2a) and Co(SnCl 3)(CO) 2[PPh(OEt) 2] 2 (2b) derivatives. Trichlorogermyl complexes Co(GeCl 3)(CO) 2L 2 (3, 4) [L = PPh 3, PPh(OEt) 2] were prepared by allowing halo compounds CoX(CO) 2L 2 (X = Cl, I) to react with GeCl 2·dioxane. Treatment of trihalostannyl complexes Co(SnCl 2X)(CO) 2L 2 (1, 2) (X = Cl, I) with NaBH 4 in ethanol yielded tin trihydrido derivatives Co(SnH 3)(CO) 2L 2 (5, 6). Instead, reaction of Co(SnCl 2X)(CO) 2[PPh(OEt) 2] 2 (2) with LiAlH 4 in THF yielded the hydrido CoH(CO) 2[PPh(OEt) 2] 2 (7). Trimethylstannyl Co(SnMe 3)(CO) 2L 2 (8, 9) and trialkynylstannyl derivatives Co[Sn(C≡CPh) 3](CO) 2L 2 (10, 11) were prepared by allowing trihalostannyl compounds Co(SnCl 2X)(CO) 2L 2 (1, 2) to react with MgBrMe and with Li +(PhC≡C) -, respectively, in THF. The complexes were characterised by spectroscopy (IR and 1H, 31P, 13C, 119Sn NMR) and by X-ray crystal structure determination of Co(SnCl 2X)(CO) 2[PPh(OEt) 2] 2 (2) and Co(GeCl 3)(CO) 2[PPh(OEt) 2] 2 (4). © 2012 Elsevier B.V. All rights reserved.